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Studies on Sintering and Grain Growth in Magnesium

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Studies on Sintering and Grain Growth in Magnesium STUDIES ON SINTERING AND GRAIN GROWTH IN MAGNESIUM by CHRISTOPHER PAUL BURDESS, B.Sc.,A.R.C.S. A Thesis submitted for the Degree of Doctor of Philosophy in the University of London. August 1966 Chemistry Department, Imperial College of Science and Technology, LONDON S.W.7. ABSTRACT. Pure magnesium oxide (1200 ppm metallic impurities) was prep- ared by calcining pure magnesium oxalate which. had been produced by mixing purified solutions of magnesium nitrate and ammonium oxalate. The hydration characteristics in air atmospheres at different relative humidities were studied in order that the effect on sint- ering of dehydration might be estimated. The rate of hydration of magnesium oxide is discussed. Infra-red spectrophotometric studies were made in order that the surface conditions might be better known. The sintering of pure magnesia was studied, and found not to obey the semilogarithmic densification law found by other workers. Data for two successive smaller ranges of densification gave two activation energies, comparable however with. those obtained by other workers who applied the semilogarithmic densification laws to the whole range of densification. The grain growth during the sintering of pure magnesium oxide of small initial particle size was found to occur in two stages, at least on the surface, and probably also in the bulk of the material. An initial stage, characterised by growth from nuclei, and obeying a grain size o< time law (probably discontinuous grain' growth), was n followed by normal grain growth, characterised by a (grain size) o< time law, where n is close to 2. Other types of grain groW-th and other effects during. sintering and grain growth were examined microscopically and by electron microprobe analysis. I Dedicate this Thesis to my Grandmother, Mrs. Mabel Burdess. CONTEUTS Chapter 1. Introduction and Literature Survey 1 Chapter 2. Experimental Techniques 87 Chapter 3. Pure Magnesium Oxide 102 Cha:oter 4. Sintering 151 Chapter 5. Grain Growth 177 Chapter 6. Discussion 214 References 233 Acknowledgements 246 CHAPTER 1. Introduction and Literature Survey. 1.1. Introduction 2 1.2. Sintering - Phenomena and Mechanisms 3 (a) Early Observations on Sintering 3 (b) The VisOoub Flow Model 5 (c) Neck Growth. Relations for Sintering Models 8 (d) Evidence for Diffusion in Microcreep experiments 14. (e) Diffusion in Sintering 14. (f) Sintering Ionic and Covalent Solids 16 (g) Grain Boundaries as Vacancy Sinks 18 (h) Further Treatment of Model Systems 19 (i) Role of Grain Boundaries in Vacancy Annihilation 26 (j) Diffusion Mechanisms and Sintering 28 (k) Diffusion paths in Sintering 29 (1) The Intermediate Stage Sintering Models 36 (m) Further Work on the Sintering of Oxides 39 (n) Revision of the Initial Stage Sintering Model 41 Co) Further Work on the Intermediate Stage of Sintering 43 (p) Recent Work on Diffusion and Sintering in Oxides 49 1.3. The Effect of Additives and Atmospheres on Sintering 51 (a) Introduction 51 (b) The Importance of Solid Solutions 53 (c) Surface Effects and Solid Solutions 54- (d) The Effect of Atmospheres 59 (e) The Effect of Water-vapour on Sintering of Oxides 61 1.4. Hydration of Magnesium Oxide 62 1.5. Grain Growth 66 (a) Introduction and Early Observations 66 (b) The Importance of Crystallographic Orientation 70 (c) The Mechanisms of Grain Growth 71 (d) The Effect of Inclusions 73 (e) Work with. Pure Metals 74 (f) Theoretical Anpects 75 (g) Grain Growth in Non-metals 76 (h) The Effect of Grain Boundaries and Pores on Grain Growth 82 1.6. Broad Conclusions from Previous Work; Fields for Further Research PO, 85 - 2 - 1.1. INTRODUCTION. A set of small particles has a greater-free energy than a large particle of the same volume, because of the greater surface energy arising from the surface area difference. Similarly, a particle con- sisting of numerous crystals of different orientations, separated from each other by grain boundaries, has a greater free energy than a single crystal. Under appropriate conditions, the small particles may agglomerate and densify to a body of smaller surface area, and the body may further reduce its free energy by conversion to a single crystal. Fass and White (1966) have obtained a single crystal of cadmium sulphide by such a process - sintering a powder compact - but it is more usual for sintered products to contain solid-vapour and solid-solid boundaries (pores and grain boundaries). Sintering and grain growth occur in the formation of metamorphic rocks: the rocks are eroded to small particles, sedimented in estuaries etc., and pressed at high pressures and heated for long times during g..64.0... logical upheaval. The process may be seen in the review of Voll (1960) on observations- of geological grain growth. The procesS of sintering with a liquid phase between the particles, in the form of pottery manufacture, has been known for some 5,000 years, but it was not until comparatively recently that the sintering of pure crystalline solids, without a liquid phase being present, was considered possible, and even then, sintering was considered difficult (Crone and McKee, 1950). Liquid phase sintering, afritting", is not considered in detail in this review, and the reader is referred to Jones (1960) and Kingery (1959). 2 The surface energy of magnesium oxide is about 1150 ergs/cm . (Jura and Garland, 1952; Livey and Hurray, 1956; Gilman, 1960; Westwood and Goldheim, 1963). The excess free energy, d G, of a powder of diameter particles is about o.46 cal/g (145 cal per mole) above that of a single crystal, and for 200A particles AG-23cal/g, (920 cal/mole). 3 - The major proportion of this free energy is available for sintering, in which the small particles change shape and consolidate together so that their surfaces become grain boundaries, and the remainder is available for grain growth, where the total grain boundary area is reduced. The proportions depend on the relative values of the surface and grain boundary energies. While it is easy to separate sintering and grain growth in theory, in practice the two phenomena are related, and grain growth may occur before sintering is complete. During sintering, material transport may occur by any one or a combination of the following mechanisms: (1) Viscous or other macroscopic flow, (2) Evaporation-condensation, (3) Volume, grain boundary or surface diffusion, though not all the possible mechanisms have been recognised from the start of work on the theoretical aspects of sintering. 1.2. SINTERING - 1),IIEN0rjalA AND AILHANISMS. (a) Early Observationsi on Sintering. An observation by Faraday (1857) that a gold leaf mounted on glass and heated to 500°C lost its green colour and became transparent, reap- pearing on burnishing, was explained by Turner (1908) as a breaking-down of the continuous foil into a network of gold strands, which flatten out somewhat on burnishing. This ability of a material to decrease its surface area at temperatures below the melting point had been used in the process developed in the early 18th century for the consolidation of platinum sponge. The investigations into the properties of finely-divided noble metal and other catalysts early this century brought interesting observations on sintering. Wright and Smith (1921) noted the decrease in specific surface which accompanied sintering in the conversion of platinum black to grey - 4 - and white platinum, and noted that mounting on asbestos preserved the platinum black longer at high temperatures, ascribing this reduction of sintering to the reduced inter-particle contact. The cause of sintering was thought to be the property which also caused increased vapour pressure and solubility of small particles. Smith (1923) considered that any lowering of the melting-point of a substance due to diminution of particle size was unlikely to be more than a fraction of a degree,so the material must certainly be solid at the time of sintering. Polished surfaces were thought at that time to consist of a layer of amorphous material on top of the main crystalline mass, and it was reported that such "amorphous" surfaces sintered more readily than crystalline ones, though the sig- nificance of a greater area of contact was recognised. It was also found that fine iron powders sintered most readily at temperatures known to correspond to phase transformations. Hedvall (1922), in investigations of colour changes on heating iron oxides, noted the spheroidisation of haematite platelets, and the coalescence of small particles into large ones on heating. Work by Roberts-Austin (1896) on the diffusion of gold in lead, and by Groh and von Hevesy (1920) on the self-diffusion of lead, showed the possibility of diffusion in solids, and the work of Tammann (1921) and Endell (1922) on the growth of reaction layers and on reactions in solid powders showed the applicability of diffusion to solid state reactions. Sauerwald (1923) suggested a "sintering temperature" of about two-thirds of the absolute me ting-point, but the experiments of Tammann and Mansuri (1923), using a paddle-wheel, driven via a friction clutch, revolving in a drum of powder, did not reveal the "sintering temperature" at which the paddle--wheel stopped as being 5 a significant fraction of the melting-point in the same way as the "Tammann temperature" was held to be significant for diffusion. Muller (1935) showed, in effect, that on isothermal sintering the strength of a rock-salt compact first increased, owing to neck formation between the particles, and then, at longer times, the strength decreased owing to grain growth in the compact. li Huttig (1942) considered that surface diffusion was responsible for the initial stage of sintering. It was in attempts to verify one or other of the various possible material transport mechanisms that the subsequent theoretical treatments of model systems ensued.
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